2-(1, 3, 3-trimethylbutyl)-5, 7, 7-trimethyl octanol-1-sulfate



Patented Oct. 6, 1 953 2- (1,3,3-TRIMETHYLBUTYL) -5,7,7-TRI- DIETHYL OCTANOL-l-SULFATE Albert A. Pavlic, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application May 6, 1950, Serial No. 160,587

2 Claims.

This invention relates to novel, highly branched, sulfated primary octadecyl alcohol compositions which are of value as surface-active agents. This application is a continuation-inpart of my copending application S. N. 791,939, filed December 1'7, 1947, now abandoned.

For many years, important uses have existed for relatively high molecular weight alcohols, particularly those containing about 18 carbon atoms per molecule. To meet these important needs,- especially in the detergent field, straightchain alcohols have been manufactured on a rather large scale by hydrogenation of fatty acids or esters. The literature contains apparently conflicting statements as to the relative merits .of straight chain versus branched chain alcohols as intermediates for making surface-active agents. (Compare French Patent 805,706 and A. P. C. patent application S. N. 369,507 with U. S. 2,422,613 and Ind. Eng. Chem. 35, 111 (1943). The very highly branched chain primary alcohols, with which the present invention is concerned, were not known prior to my invention,

and they had not been investigated as possible detergent intermediates prior to my invention. The question whether these very highly branched, primary alcohols could be employed successfully in place of the previously-known, longchain alcohols in the manufacture of sodium alkyl sulfate surface-active agents therefore remained unanswered.

An object of the present invention is to provide, from readily available sources, a sulfated, primary alcohol which is suitable for use as a surface-active agent, and which is useful for other purposes. Other objects of the invention will appear hereinafter.

The present invention provides, as a novel composition of matter, a sulfated, highlybranched primary octadecanol; the invention is based in part upon the discovery that the nonylheptylmethyl primary carbinols of the formula (C9H19)(C'1H15)CH-CH2OH have outstanding properties as intermediates for high speed wetting agents. This octadecyl alcohol composition thus differs from previously known higher alcohols in a. surprising manner. Since this octadecanol is much more highly branched than any of the previously disclosed primary alcohols of similar molecular weight, it is indeed quite remarkable that it nevertheless can be converted to a sodium alkyl sulfate which has outstanding properties as a high speed wetting agent, and which, in fact, is far superior in wetting power to the best previously known straight-chain sodi- 2 um alkyl sulfates of similar molecular weight in that it is readily soluble in organic solvents. For example, it dissolves readily in hydrocarbons such as benzene which are non-solvents for the straight-chain sodium alkyl sulfonates.

The highly branched octadecanol of this invention is obtained by a process represented by the following equations:

3,5,5-Trimethylhexana1 Aldol condensation product (Nonyl aldehyde) Aldol condensation product CsHi1CHzCH(C1Hi5)CH:OH

Octadecyl alcohol Preparation of 3,5,5-trimethylhexanal is disclosed in copending application S. N. 758,477, filed July 1, 1947, now abandoned. This aldehyde is obtained by reacting carbon monoxide and hydrogen with diisobutylene in the presence of a. cobalt catalyst at elevated temperatures and pressures (cf. S. N. 598,208, filed June 7, 1945, now Patent No. 2,437,600). The structural formula of the chief aldol condensation products of 113,5,5-trimethylhexanal can be represented as folows:

Hydrogenation of the latter condensation product converts the CH0 group to methylol. Thus the monohydric primary octadecanol obtained in the practice of this invention is a. nonylheptyl methyl primary carbinol,

(C9H19) (C'IH15)CH-CH2OH The main ingredient evidently has the structure 5 cm on, E10 CH; cm CHz()-CH47HOH:CHz-$H'IHCH:-CH:

i. e. it is 2-(l,3,3-trimethylbutyl)-5,'7,'7-trimethyloctanol-l. The invention is illustrated further by means of the following example.

ErampZe.A mixtu'ie of 1611.0 grams (11.35 mols) of 3,5,5-trimethylhexanal and 100.0 grams (5.6% by weight) of piperidine acetate catalyst was heated at 98 C. with stirring during 7 hours. After standing during 63 hours at 98 C. the re action mixture was distilled under reduced pressure. The fraction boiling in the range 124 to 140 C./4.5 mm. amounted to 855 grams, corresponding to a 56.6% conversion to octadecenal.

Most of this aldol condensation product (weight 842 grams) was hydrogenated with 5.3% by weight of nickel-on-kieselguhr as catalyst. Hydrogenation was conducted at 700 atmospheres pressure, 155 to 160 C. during one hour. Fractional distillation of the combined filtered reaction mixture resulted in 661 grams of product boiling over the range 120 to 148 C./6 mm. and varying in refractive index (11, from 1.4510 to 1.4502. This weight corresponds to a conversion of 83%. Further purification was effected by a rehydrogenation treatment followed by a distillation recovery, resulting in octadecyl alcohol of hydroxyl number=206.0 (99+%), free carbonyl number:0.0, combined carbonyl number:3.0. The purified octadecyl alcohol was a water-white oil of refractive index boiling point 146/7 mm. or 141 C./3 mm. It was insoluble in water, but was soluble in methanol, ethanol, acetone, benzene, cyclohexane, and dioxane. This octadecyl alcohol was converted to the sodium alkyl sulfate by reaction with an equimolar quantity of chlorosulfonic acid followed by neutralization with sodium hydroxide. The reaction with chlorosulfonic acid was carried out by slowly adding the chlorosulfonic acid to the alcohol at 25 to 40 .C. with stirring. The sodium alkyl sulfate thus obtained (namely sodium 2 (1,3,3-trimethy1butyl) -5,7,7 trimethyloctanol-l sulfate) was tested to determine its wetting power, i. e. the minimum concentration (grams/liter) in water which is required to cause a standardized skein of cotton to sink in .25 seconds. Comparative tests were made with wellknown commercial surface-active agents. The results were as follows:

The tests with soft water set forth in the example show that the sodium octadecyl sulfate prepared from the octadecanol of this invention is more effective in wetting cotton than the best commercially available surface-active agents.

It is to be understood that the foregoing example is illustrative only and that it should not be considered as limiting the invention. In the "preparation of the C9 aldehyde by carbonylation of diisobutylene, any suitable hydrogenation catalyst may be employed, as disclosed in copending application S. N. 598,208, filed June 7, 1945. Similarly, the aldol condensation of the C9 aldehyde can be efiected by means of any suitable catalyst, e. g. any alkaline substance. Any suitable hydrogenation catalyst may be employed in the hydrogenation of the aldol condensation product. The sulfation of the alcohol can be carried out by any suitable method, such as by reacting the alcohol at 25 to C. for about one hour with dioxane-SOe complex (formed by passing gaseous sulfur dioxide into a chilled mixture of dioxane and ethylene dichloride). and the neutralization of the sulfate may be accomplished by employing ammonia, ethanolamine, diethanolamine, triethanolamine, morpholine, lime, calcium carbonate, magnesia, magnesium carbonate, alkali metal hydroxides orany other similar neutralizing agent. Dilute neutralizing agents, e. g. 3% NaOH in water, are preferred. The sodium octadecyl sulfate can be isolated readily in the form of a dry, white, rather flaky watersoluble solid, by evaporation of water from the neutralized sulfated product. Since the procedure for condensation of the C9 aldehyde, hy-

drogenation of the resulting aldol condensation product and sulfation of the resultant alcohol may be varied rather widely without altering the properties of the octadecanol sulfate thus obtained, it is to be understood that I do not limit myself except as set forth in the following claims.

I claim:

1. A 2-(1,3,3-trimethylbutyl) 5,7,7-trimethyloctanol-l sulfate.

2. Sodium 2 (1,3,3 trimethylbutyl) 5,7,7- trimethyloctanol-l sulfate.

ALBERT A. PAVLIC.

Ser. NO. 369,507, Roelen (A. P. 0.), published July 13, 1943. 

1. A 2-(1,3,3-TRIMETHYLBUTYL) - 5,7,7-TRIMETHYLOCTANOL-1 SULFATE. 